{"title":"SmI2- 介导化学中的光：合成应用和机理研究","authors":"Subhasmita Patra, Sipramayee Satapathy, Aswini Rath, Akash Kumar Nayak, Sandeepan Maity","doi":"10.1002/poc.4570","DOIUrl":null,"url":null,"abstract":"<p>SmI<sub>2</sub> is a versatile reagent in single electron transfer-mediated reductive transformations. Photoexcitation of SmI<sub>2</sub> generates a reactive excited state capable of transferring an electron to substrates that are recalcitrant towards accepting electrons. Synthetic results unequivocally indicate light as a green and sustainable promoter of SmI<sub>2</sub>-mediated chemistry, with the potential to replace the suspected carcinogen hexamethylphosphoramide (HMPA). Rate constants of photoinduced electron transfer from SmI<sub>2</sub> are in the range of 10<sup>7</sup>–10<sup>9</sup> M<sup>−1</sup> s<sup>−1</sup>, which are an order of magnitude higher in comparison with the ground state process. Recent advancement in Eu<sup>II</sup>- and Ce<sup>III</sup>-based photo-redox catalysis rejuvenated the area of photo-catalyzed reactions of low-valent lanthanides. This review article aims to illustrate the role of photoexcitation on SmI<sub>2</sub>-mediated reductive transformations.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":1.9000,"publicationDate":"2023-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Light in SmI2-mediated chemistry: Synthetic applications and mechanistic studies\",\"authors\":\"Subhasmita Patra, Sipramayee Satapathy, Aswini Rath, Akash Kumar Nayak, Sandeepan Maity\",\"doi\":\"10.1002/poc.4570\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>SmI<sub>2</sub> is a versatile reagent in single electron transfer-mediated reductive transformations. Photoexcitation of SmI<sub>2</sub> generates a reactive excited state capable of transferring an electron to substrates that are recalcitrant towards accepting electrons. Synthetic results unequivocally indicate light as a green and sustainable promoter of SmI<sub>2</sub>-mediated chemistry, with the potential to replace the suspected carcinogen hexamethylphosphoramide (HMPA). Rate constants of photoinduced electron transfer from SmI<sub>2</sub> are in the range of 10<sup>7</sup>–10<sup>9</sup> M<sup>−1</sup> s<sup>−1</sup>, which are an order of magnitude higher in comparison with the ground state process. Recent advancement in Eu<sup>II</sup>- and Ce<sup>III</sup>-based photo-redox catalysis rejuvenated the area of photo-catalyzed reactions of low-valent lanthanides. This review article aims to illustrate the role of photoexcitation on SmI<sub>2</sub>-mediated reductive transformations.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2023-09-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4570\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4570","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Light in SmI2-mediated chemistry: Synthetic applications and mechanistic studies
SmI2 is a versatile reagent in single electron transfer-mediated reductive transformations. Photoexcitation of SmI2 generates a reactive excited state capable of transferring an electron to substrates that are recalcitrant towards accepting electrons. Synthetic results unequivocally indicate light as a green and sustainable promoter of SmI2-mediated chemistry, with the potential to replace the suspected carcinogen hexamethylphosphoramide (HMPA). Rate constants of photoinduced electron transfer from SmI2 are in the range of 107–109 M−1 s−1, which are an order of magnitude higher in comparison with the ground state process. Recent advancement in EuII- and CeIII-based photo-redox catalysis rejuvenated the area of photo-catalyzed reactions of low-valent lanthanides. This review article aims to illustrate the role of photoexcitation on SmI2-mediated reductive transformations.
期刊介绍：
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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